Memory element and memory device

ABSTRACT

A memory element with a first electrode, a memory layer, and a second electrode in this order. The memory layer includes a resistance change layer provided on the first electrode side, an ion source layer provided on the second electrode side, an intermediate layer provided between the resistance change layer and the ion source layer, and a barrier layer provided at least either between the ion source layer and the intermediate layer, or between the intermediate layer and the resistance change layer.

RELATED APPLICATION DATA

This application is a continuation of U.S. patent application Ser. No.13/416,502 filed Mar. 9, 2012, the entirety of which is incorporatedherein by reference to the extent permitted by law. The presentapplication claims the benefit of priority to Japanese PatentApplication No. JP 2011-061628 filed on Mar. 18, 2011 in the JapanPatent Office, the entirety of which is incorporated by reference hereinto the extent permitted by law.

BACKGROUND

The present disclosure relates to a memory element and a memory devicestoring information based on any change of electrical characteristicsobserved in a memory layer including an ion source layer and aresistance change layer.

SUMMARY

A semiconductor nonvolatile memory popularly used for data storage hasbeen a NOR or NAND flash memory. As for such a semiconductor nonvolatilememory, many attempts have been made to increase the capacity thereof bythe microfabrication of memory elements and drive transistors therein.However, the semiconductor nonvolatile memory has been pointed out thatthere are limitations on microfabrication considering the need for ahigh level of voltage for writing and erasing, and the limited number ofelectrons injected into a floating gate.

For overcoming such limitations on the microfabrication, anext-generation nonvolatile memory currently proposed is a resistancechange memory such as ReRAM (Resistance Random Access Memory) or PRAM(Phase-Change Random Access Memory) (for example, see JapaneseUnexamined Patent Application Publication No. 2006-196537, and Waser et.al., Advanced Material, 21, p2932 (2009)). These memories are each inthe simple configuration including a resistance change layer between twoelectrodes. In the memory of Japanese Unexamined Patent ApplicationPublication No. 2006-196537, as an alternative to the resistance changelayer, an ion source layer and an oxide film (thin film for storage) areprovided between first and second electrodes. These resistance changememories are each formed therein with a conductive path throughmigration of atoms or ions by heat or an electric field, whereby aresistance value is supposed to change.

However, if a nonvolatile memory is microfabricated as such, thetransistors driving the memory elements show a tendency to be decreasedin drive current. However, the memory elements show a tendency to beincreased in resistance as a result of the reduction of the area takenup thereby. As such, microfabricating the nonvolatile memory decreasesthe drive current of the transistors but the smaller memory elementscause the increase of writing current and voltage. This results in afailure of sufficient writing and erasing, thereby causing adisadvantage of reducing the element characteristics.

It is thus desirable to provide a memory element and a memory devicewith improved writing and erasing characteristics during operations at alow voltage and a low current.

A memory element according to an embodiment of the present disclosureincludes a first electrode, a memory layer, and a second electrode inthis order. The memory layer includes a resistance change layer providedon the first electrode side, an ion source layer provided on the secondelectrode side, an intermediate layer provided between the resistancechange layer and the ion source layer, and a barrier layer provided atleast either between the ion source layer and the intermediate layer, orbetween the intermediate layer and the resistance change layer, and thebarrier layer containing a transition metal or a nitride thereof.

A memory device according to another embodiment of the presentdisclosure includes a plurality of memory elements, and a pulseapplication section. The memory elements each include a first electrode,a memory layer, and a second electrode in this order, and the pulseapplication section applies a voltage or current pulse selectively tothe memory elements. In the memory device, the memory elements are eachthe memory element according to the embodiment of the presentdisclosure.

With the memory element (memory device) according to the embodiments ofthe present disclosure, after the memory layer is formed, movable ions(metal ions) in the ion source layer diffuse into the intermediatelayer, and then move onto the first electrode for oxidation. Theoxidized metal ions form an oxide film, i.e., a resistance change layer,so that the resulting memory element is put in the initial state with ahigh resistance, i.e., in the high-resistance state. When voltage orcurrent pulses of “positive direction” (e.g., the first electrode sideis at a negative potential, and the second electrode side is at apositive potential) are applied with respect to the element in theinitial state (high-resistance state) as such, the first electrodeserves as a cathode electrode, and the metal ions contained in the ionsource layer or in the intermediate layer are moved to the resistancechange layer. The metal ions then become almost in the form of metal bybonding with electrons in the resistance change layer on the firstelectrode as a result of a reduction reaction thereon. Alternatively,the oxide film itself forming the resistance change layer is reduced andresulted in a defect, thereby forming an impurity level. As a result, alow-resistance section (conductive path) containing the metallic elementis formed in the memory layer, thereby decreasing the resistance of theresistance change layer (state of recording). When current pulses of“negative direction” (e.g., the first electrode side is at a positivepotential, and the second electrode side is at a negative potential) areapplied with respect to the element in the low-resistance state as such,the first electrode serves an anode electrode. This thus causes anoxidation reaction, and the conductive path made of the metallic elementin the form of metal is ionized, and then is dissolved into the ionsource layer. Or an oxide film is formed by the active metallic elementbonding with oxygen therearound between the intermediate layer and thefirst electrode so that the resistance change layer is increased inresistance (initial state or state of erasing).

Herein, by providing the barrier layer containing a transition metal ora nitride thereof at least either between the ion source layer and theintermediate layer or between the intermediate layer and the resistancechange layer, any excessive movement of the metal ions is to befavorably prevented.

According to the memory element and the memory device in the embodimentsof the present disclosure, the barrier layer containing a transitionmetal or a nitride thereof is provided at least either between the ionsource layer and the intermediate layer or between the intermediatelayer and the resistance change layer. This accordingly prevents movableions from excessively moving after the formation of the memory layer orduring voltage application, thereby preventing any excessive increase ofa resistance value. In other words, the writing and erasingcharacteristics are favorably improved.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary, and are intended toprovide further explanation of the technology as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a furtherunderstanding of the disclosure, and are incorporated in and constitutea part of this specification. The drawings illustrate embodiments and,together with the specification, serve to explain the principles of thetechnology.

FIG. 1 is a cross-sectional view of a memory element in an embodiment ofthe present disclosure, showing the configuration thereof.

FIG. 2 is a cross-sectional view of a memory cell array using the memoryelement of FIG. 1, showing the configuration thereof.

FIG. 3 is a plan view of the memory cell array of FIG. 2.

FIG. 4 is a cross-sectional view of a memory element in a modificationof the present disclosure, showing the configuration thereof.

FIGS. 5A to 5F are diagrams of resistance distribution in the respectiveexperimental samples.

FIGS. 6A to 6F are also diagrams of resistance distribution in therespective experimental samples.

FIGS. 7A and 7B are diagrams showing the data retention characteristicsin the respective experimental samples.

FIGS. 8A and 8B are each a characteristics diagram showing arelationship between the element resistance and the film thickness of abarrier layer.

FIGS. 9A and 9B are each a characteristics diagram showing also therelationship between the element resistance and the film thickness ofthe barrier layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

In the below, by referring to the accompanying drawings, an embodimentof the present disclosure is described in the following order.

(Embodiment)

1. Memory Element (Memory Element with Barrier Layer disposed betweenIon Source Layer and Intermediate Layer)

2. Memory Device

(Modification)

(Memory Element with Barrier Layer disposed between Intermediate Layerand Resistance Change Layer)

EXAMPLES

(Embodiment)

(Memory Element)

FIG. 1 is a cross-sectional view of a memory element 1 in an embodimentof the present disclosure, showing the configuration thereof. Thismemory element 1 is configured to include a lower electrode 10 (firstelectrode), a memory layer 20, and an upper electrode 30 (secondelectrode) in this order.

The lower electrode 10 is provided on a silicon substrate 41 formed witha CMOS (Complementary Metal Oxide Semiconductor) circuit as will bedescribed later (FIG. 2), for example, thereby serving as a connectionsection with the portion of the CMOS circuit. This lower electrode 10 ismade of a material for wiring use in the semiconductor process, e.g.,tungsten (W), tungsten nitride (WN), copper (Cu), aluminum (Al),molybdenum (Mo), tantalum (Ta), and silicide. When the lower electrode10 is made of a material such as Cu that possibly causes ion conductionin an electric field, the surface of the lower electrode 10 made of Cuor others as such may be covered with a material that hardly causes ionconduction or thermal diffusion, e.g., W, WN, titanium nitride (TiN),and tantalum nitride (TaN). When an ion source layer 21 that will bedescribed later contains Al, preferably used is a metal film containingat least one of chromium (Cr), W, cobalt (Co), Si, gold (Au), palladium(Pd), Mo, iridium (Ir), titanium (Ti), and others that are moreresistant to ionization than Al, or an oxide or nitride film thereof.

The memory layer 20 in this embodiment includes the ion source layer 21,a barrier layer 22, an intermediate layer 23, and a resistance changelayer 24, which are disposed one on the other in this order from theupper electrode 30 side. The ion source layer 21 contains elements forforming a conductive path in the resistance change layer 24, i.e., anelement to be converted into cations, and an element that is possiblyanionized. Note that the movable ions (metal ions) described above arecations in this example. The element that is possibly cationizedincludes one or two or more of metallic elements such as Cu, Al, silver(Ag), and zinc (Zn). An ion conductive material that is to be anionizedincludes at least one or more of chalcogen elements including tellurium(Te), sulfur (S), and selenium (Se), or may include oxygen (O). The ionsource layer 21 in this example is disposed to be in contact with theupper electrode 30. The metallic element(s) and the chalcogen element(s)are bonded together, thereby forming a metal chalcogenide layer. Thismetal chalcogenide layer is mainly in the amorphous structure, andserves as an ion supply source.

The metallic element that is possibly cationized moves in the ion sourcelayer 21 or in the intermediate layer 23 during the operation ofwriting, and is reduced on the cathode electrode, thereby forming aconductive path (filament) in or almost in the form of metal. As such,considering to be movable in the ion source layer 21 or in theintermediate layer 23, the metallic element is preferably Cu, Al, Ag,Zr, and others described above. Considering to be chemically stable toremain in the form of metal in the ion source layer 21 containing thechalcogen element(s) described above, the metallic element may betransition metals of groups 3 to 11 in the periodic table other thanthose described above, for example. Among these elements, one or two ormore are possibly used. Alternatively, silver (Ag) and Si or others maybe used as additive elements to the ion source layer 21. Among thetransition metals described above, for stabilization of the conductivepath and for adjustment of resistivity of the ion source layer 21described above, any of the following may be specifically usedpreferably, i.e., zirconium (Zr), hafnium (Hf), titanium (Ti), Mo, W,niobium (Nb), and Ta, and platinum (Pt), Cr, manganese (Mn), and iron(Fe) may be also used.

The specific material of the ion source layer 21 as such containsZrTeAl, TiTeAl, CrTeAl, WTeAl, TaTeAl, and others. Such specificmaterials may also include CuZrTeAl being a result of addition of Cu toZrTeAl, CuZrTeAlGe being a result of addition of Ge to CuZrTeAl, andCuZrTeAlSiGe being a result of addition of another additive element toCuZrTeAlGe. Another option is ZrTeMg including Mg as an alternative toAl. As for the metallic element configuring the ion source layer 21, anysimilar additive element is possibly used even if a transition metalelement selected for use is not Zr but Mo, Mn, or Hf, e.g., possiblyCuMoTeAl, and CuMnTeAl. Moreover, as for the ion conductive material, Teis surely not restrictive, and S, Se, or iodine (I) may be also used,i.e., specifically ZrSAl, ZrSeAl, ZrlAl, CuGeTeAl, and others, and Ta,W, or others may be added.

Note that the ion source layer 21 may be added with any other elementsfor the purpose of preventing peeling of film during a high-temperatureheat treatment for the memory layer 20, for example. Si, Ge, or othersare each an exemplary additive element that possibly offers also theimprovement of retention characteristics, and is preferably added to theion source layer 21 together with Zr.

The barrier layer 22 is disposed between the ion source layer 21 and theintermediate layer 23. This barrier layer 22 serves to control themovement of movable ions (metal ions) from the ion source layer 21 tothe lower electrode 10 side. Specifically, the barrier layer 22 servesto prevent any excessive movement of the movable ions from the ionsource layer 21 to the intermediate layer 23, and to prevent anyformation of an oxide film on the surface of the lower electrode 10.With the barrier layer 22 formed as such, the memory element 1 isprevented from increasing in resistance value. The barrier layer 22preferably has the film thickness thicker than 0.1 nm but thinner than 1nm, for example. If the barrier layer 22 is not thick enough, themovable ions are not sufficiently prevented from moving. As a result, ahigh-resistant oxide film is formed on the lower electrode 10, and thisincreases the resistance value of the memory element 1. On the otherhand, if the barrier layer 22 is too thick, the resistance value of thememory element 1 is decreased, and this resultantly narrows theresistance separation width during the operation of writing and erasing,thereby impairing the data retention characteristics. The material forsuch a barrier layer 22 includes at least a transition metal or anitride thereof. The material specifically includes Cu, Ti, Zr, Hf,vanadium (V), niobium (Nb), Ta, Cr, Mo, and W.

The intermediate layer 23 is an electrolyte layer of effectivelyionizing the metallic element that is to be converted into movable ions,and facilitating the movement of the movable ions. The intermediatelayer 23 contains an ion conductive material that is to be anionized.The intermediate layer 23 is lower in conductivity than the ion sourcelayer 21, and is more ready for application of voltage bias than the ionsource layer 21 so that the movable ions are easy to move therein. Assuch, by the film thickness of the intermediate layer 23, the memoryelements 1 are to be adjusted in resistance value. To be specific, theintermediate layer 23 preferably has the film thickness of 4 nm or morebut 10 nm or less, for example. When the intermediate layer 23 is notthick enough, this diminishes the effect of facilitating the movement ofthe movable ions from the ion source layer 21 to the resistance changelayer 24. On the other hand, when the intermediate layer 23 is toothick, this enhances the effect of facilitating the movement of themovable ions from the ion source layer 21 to the resistance change layer24. As a result, the resistance value is increased too much, therebypossibly resulting in a difficulty in writing and erasing.

The intermediate layer 23 is made of a compound mainly containing Tethat behaves as an anionic component, and Al that behaves as a movablecationic component. Such a compound is exemplified by AlTe. As for themovable cationic component, not only Al but Cu, Zn, and Ag may be used,and as a compound containing such a component, CuTe, ZnTe, and AgTe maybe used. Another option is MgTe containing Mg. In the composition of thecompound containing Te as such, e.g., AlTe, the content of Al ispreferably 20 atomic % or higher but 60 atomic % or lower. As an anioniccomponent, a chalcogen element such as sulfur (S) or selenium (Se) maybe included together with Te.

The ratio of the content of aluminum (concentration of aluminum) to thecontent of the chalcogen element(s) in the intermediate layer 23 ispreferably smaller than the ratio of the content of aluminum(concentration of aluminum) to the content of the chalcogen element(s)in the ion supply layer 21. As for aluminum (Al) in the intermediatelayer 23, it is supposed to be produced by diffusion as a result of theconcentration gradient with the ion source layer 21, and thus isexpected to be smaller in content than the stoichiometric composition ofAl₂Te₃. Such aluminum (Al) in the intermediate layer 23 is supposed toexist mostly in the form of ions. Moreover, as described above, theintermediate layer 23 is lower in conductivity but higher in resistancevalue than the ion source layer 21. Accordingly, applied potential iseffectively used for driving ions so that the resulting nonvolatilememory is possibly with improved retention characteristics describedabove, and is operatable at a low current.

The resistance change layer 24 is disposed on the lower electrode 10side, and in this example, is in contact with the lower electrode 10.This resistance change layer 24 shows a change of resistance value whena predetermined level of voltage is applied between the lower and upperelectrodes 10 and 30. In this embodiment, this resistance change layer24 is in the layered structure including a semiconductor or insulatorand an oxide of movable cations, or is in the mixed structure thereof.The semiconductor or insulator is the one to be stable even if it is incontact with the intermediate layer 23. The resistance change layer 24is exemplarily made of oxide materials, oxynitride materials, or nitridematerials including at least one transition metal element including Ti,Zr, Hf, Ta, W, and others, for example. Such materials are preferable asare being stable against the cathode reaction even if the resistancechange layer 24 is in contact with the intermediate layer 23. Moreover,an oxide of Al is preferable considering that it shows a high resistancevalue, and leads to a high resistance change ratio. The intermediatelayer 23 may contain an oxide of Cu, Zn, and Ag that may be in the formof CuTe, ZnTe, and AgTe. Alternatively, when the intermediate layer 23contains MgTe, an oxide of Mg may be contained.

Herein, at the point in time when the memory layer 20 is formed, in theresistance change layer 24, TiO₂ being a semiconductor layer that isstable even if it is in contact with the intermediate layer 23 is formedon the lower electrode 10, for example. However, after the formation ofthe memory layer 20, the movable ions in the ion source layer 21 or inthe intermediate layer 23, e.g., aluminum ions, start diffusinggradually from the ion source layer 21 to the lower electrode side viathe intermediate layer 23. As a result, in the resistance change layer24, an oxide of Al is formed on TiO₂, or TiO₂ is mixed together with theoxide of Al. In other words, the resistance change layer 24 is in thelayered or mixed structure including an Al oxide film contributing tooxidation-reduction, and a layer including a semiconductor or insulatorpreventing any unnecessary oxidation-reduction such as TiO₂. Theresistance change layer 24 may be added with, other than the elementsdescribed above, a high-resistance oxide material such as Si orrare-earth oxide that increases more the resistance of the resistancechange layer 24.

The upper electrode 30 may be made of a material similar to that of thelower electrode 10, i.e., a well-known material for use of semiconductorwiring, and preferably, be made of a stable material not reacting withthe ion source layer 21 even after a post annealing treatment.

With such a memory element 1 of the embodiment, when a voltage orcurrent pulse is applied by a power supply circuit (pulse applicationsection; not shown) via the lower and upper electrodes 10 and 30, thememory layer 20 shows a change of the electrical characteristicsthereof, e.g., change of the resistance value thereof, therebyperforming information writing, erasing, and reading. In the below, suchan operation is described specifically.

First of all, a positive voltage is applied to the memory element 1 suchthat the upper electrode 30 is at a positive potential, and the lowerelectrode 10 side is at a negative potential, for example. In responsethereto, any metallic element in the ion source layer 21 is ionized andthen is diffused to the resistance change layer 24. By the cathodereaction on the lower electrode 10 side, the metallic element is thendeposited by reduction in the resistance change layer 24 to be in theform of metal through bonding with electrons. As a result, a filamentmade of the low-resistance metallic element is formed. Alternatively, bythe cathode reaction on the lower electrode 10 side, the high-resistanceoxide film in the resistance change layer 24 is reduced and resulted ina defect, thereby forming an impurity level. As a result, a conductivepath is formed in the resistance change layer 24, and this accordinglydecreases the resistance value of the memory layer 20, i.e., the memorylayer 20 shows a decrease of resistance value to be lower (to be in thelow-resistance state) than that in the initial state (in thehigh-resistance state).

Thereafter, even if the memory element 1 becomes free of voltage bystopping the application of the positive voltage thereto, the state oflow resistance is retained. This means information writing is done. Foruse in a once-writable memory device, i.e., a so-called PROM(Programmable Read Only Memory), the memory element 1 is completed withrecording only by the process of recording described above. On the otherhand, for application use in an erasable memory device, i.e., RAM(Random Access Memory), EEPROM (Electronically Erasable and ProgrammableRead Only Memory), or others, a process of erasing is expected. Duringthe process of erasing, a negative voltage is applied to the memoryelement 1 such that the upper electrode 30 is at a negative potential,and the lower electrode 10 side is at a positive potential, for example.In response thereto, the metallic element configuring the filamentformed inside of the resistance change layer 24 is ionized by the anodereaction, and then is dissolved into the intermediate layer 23 or intothe ion source layer 21. In other words, the filament disappears or isdecreased in area. Alternatively, the cyclized layer in the resistancechange layer 24 at the impurity level is oxidized by the anode reactionso that any defect in the oxide layer is repaired. Specifically, theimpurity level disappears, and the resistance value of the resistancechange layer 24 shows an increase.

Thereafter, even if the memory element 1 becomes free of voltage bystopping the application of the negative voltage thereto, the resistancevalue therein remains high. This allows erasing of any informationwritten thereto. By repeating such a procedure, the memory element 1 isto be subjected to repeated writing of information and erasing of thewritten information.

If the state high in resistance value is correlated with information of“0”, and if the state low in resistance value is correlated withinformation of “1”, for example, the information of “0” is to be changedto the information of “1” in the process of information recording by theapplication of a positive voltage, and the information of “1” is to bechanged to the information of “0” in the process of information erasingby the application of a negative voltage. Note that, in this example,although the operation of decreasing the resistance of the memoryelement is correlated with the writing operation and the operation ofincreasing the resistance thereof is correlated with the erasingoperation, the correlation may be inversed.

For demodulation of any recorded data, the larger ratio is morepreferable between an initial resistance value and an after-recordingresistance value. However, a too large resistance value of theresistance change layer 24 causes a difficulty in writing, i.e., indecreasing the resistance. As a result, since a threshold voltage forwriting is increased too much, the initial resistance value is adjustedto be 1 GΩ or smaller. The resistance value of the resistance changelayer 24 is possibly controlled by the thickness thereof or the contentof anions therein, for example.

In the embodiment, as described above, the ion source layer 21preferably contains Zr, Al, Ge, and others. The reasons are describedbelow.

When the ion source layer 21 contains Zr, Al, and Cu together with achalcogen element that is possibly anionized, the ion source layer 21possibly remains in the mechanical structure even if the movable cationssuch as Cu and Al described above are diffused into the intermediatelayer 23 so that the matrix structure is possibly kept stably. What ismore, since a fixed percentage of Zr remains in the form of metalwithout being ionized, the ion source layer 21 possibly remains high inconductivity. Zr acts as movable ions although the mobility thereof islow, and forms a conductive path in which Zr is mixed with a metallicelement such as Cu and Al being high in ion mobility. The conductivepath made of Zr reduced on the cathode electrode during the operation ofwriting is chemically stable because it is less likely to oxidize anddissolve even if being in contact with the intermediate layer 23containing a high percentage of a chalcogen element that is to beanionized. On the other hand, Cu and Al are easy to ionize in theintermediate layer 23 containing a high percentage of a chalcogenelement. However, as is easy to ionize as such, Cu and Al almost in theform of metal are likely to be less chemically stable and get easy tooxidize if it comes in contact with the intermediate layer 23.Accordingly, in the state of no application of a writing voltage pulse,i.e., in the data retention state, Cu and Al are ionized again so thatthe state transition occurs to be high in resistance. As such, the stateof low resistance is easy to retain not only with a conductive pathcontaining highly movable ions described above such as Cu and Al butalso with an ion source layer containing Zr. Moreover, combining Zr withan appropriate amount of Cu facilitates amorphization, and keeps uniformthe microstructure of the ion source layer 21, thereby contributing tothe improvement of resistance value retention characteristics.

As for the retention of the high-resistance state during the erasingoperation, exemplified now is a case where the ion source layer 21contains Al. When the intermediate layer 23 has a low concentration ofAl immediately after the memory layer 20 is formed, or when the upperelectrode 30 is biased to a negative potential as a result of theerasing operation, Al contained in the ion source layer 21 is ionized,and then moves to the resistance change layer 24 via the intermediatelayer 23, thereby forming an oxide of Al. The oxide of Al is chemicallystable even if it is in contact with the intermediate layer 23containing a high percentage of a chalcogen element, and thus remainshigh in resistance even if it is left as it is for a long time.Accordingly, any unwanted reduction reaction is less likely to occur,and under the storage in the temperature higher than the roomtemperature or under the storage for a long time, the high-resistancestate is kept as it is. This also contributes to the increase of therepetition frequency considering the self-reproduction of the resistancechange layer. Herein, Ge or others may be also used for the purpose ofstabilizing the matrix structure of the ion source layer 21, or ofpreventing film peeling.

As such, when the ion source layer 21 contains Zr, Al, Cu, Ge, andothers, compared with the previous memory element, the resulting memoryelement has the improved characteristics of wide-range resistance valueretention and of high-speed operation of writing and erasing, and theincreased repetition frequency. Moreover, if any resistance stateintermediate between high and low is created through adjustment of anerasing voltage during a change of resistance from low to high, forexample, the resulting intermediate state is to be retained with a goodstability. Accordingly, the resulting memory is capable not only ofbinary storage but also of multilevel storage. Herein, such anintermediate state is possibly created also by controlling the state ofoxidization for the resistance change layer 24 by changing a writecurrent during a change of resistance from high to low.

Moreover, other than Zr, using the transition metal elements describedabove, especially Hf, Mo, W, Nb, Ta, Pt, Cr, Mn, and Fe, favorablystabilizes the microstructure of the ion source layer 21, therebyleading to better retention of a filament, i.e., improving thelow-resistance state retention characteristics of the resistance changelayer 24.

In the below, the manufacturing method of the memory element 1 in theembodiment is described.

First of all, on a substrate formed with a CMOS circuit such asselection transistor, the lower electrode 10 made of TiN is formed, forexample. Thereafter, if appropriate, any oxides or others on the surfaceof the lower electrode 10 are removed by reverse sputtering, forexample. Next, the formation of layers is performed up to the upperelectrode 30 including the resistance change layer 24, the intermediatelayer 23, the barrier layer 22, and the ion source layer 21 insuccession through exchange of targets in a device for sputtering. Thetargets herein are those each with the composition adapted for thematerial of the corresponding layer. The diameter of the electrode is 50to 300 nmφ. A film of alloy is formed at the same time using a target ofa component element.

After the formation of layers up to the upper electrode 30, a wiringlayer (not shown) is formed for connection to the upper electrode 30,and a contact section is connected to achieve a common potential amongall of the memory elements 1. Thereafter, the layered film is subjectedto a post annealing treatment. As such, the memory element 1 of FIG. 1is completed.

In this memory element 1, as described above, a voltage is so appliedthat the upper electrode 30 is at a positive potential and the lowerelectrode 10 is at a negative potential, thereby forming a conductivepath in the resistance change layer 24. This accordingly decreases theresistance value of the resistance change layer 24 so that writing isperformed. Next, to each of the upper and lower electrodes 30 and 10,applied this time is a voltage whose polarity is opposite to thatapplied thereto for writing. In response thereto, the metallic elementin the conductive path formed inside of the resistance change layer 24is ionized again, and then is dissolved into the intermediate layer 22or the ion source layer 21. This accordingly increases the resistancevalue of the resistance change layer 24, or makes disappear the impuritylevel as a result of the defect in the oxide film in the resistancechange layer 24 so that the resistance value is increased and theoperation of erasing is performed.

As a result of the capacity increase of the resistance change memory,i.e., as a result of the microfabrication of the memory element 1, thedrive transistor is decreased in current value. Therefore, forincreasing the capacity of the resistance change memory, preventing theincrease of the operation current value of the memory element 1 isimportant. To be specific, the operation current value is expected to be100 μA or smaller considering the decreased current of the drivetransistor as a result of the microfabrication and the strength ofdiodes.

The current value at the time of changing the state of the resistancechange memory to low resistance (to the state of writing) is possiblycontrolled by changing the drive current value of the transistor. Inother words, by reducing the drive current value of the transistor, thecurrent value that puts the resistance change memory to thelow-resistance state may be prevented from increasing. However, theconductive path to be formed during writing of data is in the state ofinadequate reduction, i.e., is not reduced to be in the form of metal,and thus is likely to be oxidized again and increased in resistance.Moreover, the conductive path is not stable as is narrower in widthcompared with a metal filament to be formed during writing of data witha high current value.

Moreover, for preventing the current value from increasing when theresistance change memory is changed in state to high resistance (to thestate of erasing), similarly to the case of writing of data, thetransistor may be decreased in drive current value. Note here that ifthe transistor is low in drive voltage, this makes obvious the influenceof reducing the heat generation in the resistance change memory, and ofdividing the voltage to unnecessary portions of the transistor or of theresistance change memory, whereby the operation margin abruptly drops.

The previous memory element is in the configuration of “lowerelectrode/lower electrode oxide film (resistance changelayer)/intermediate layer/ion source layer/upper electrode”, forexample. In such a memory element, movable ions coming from the ionsource layer, e.g., Al ions, move to the surface of the lower electrodevia an intermediate layer where ion conduction occurs with more easethan the ion source layer. Immediately after the memory layer is formed,the movable ions having reached the surface of the lower electrode areoxidized so that an oxide film high in resistance is formed. In theresistance change layer being in contact with the surface of the lowerelectrode, due to the oxidation-reduction reaction of the movable ionsor the oxidation-reduction reaction of the oxide film of the movableions, a conductive path is formed, and at the same time, the oxide filmis decreased in area so that the resistance change layer shows a changeof resistance value. In the intermediate layer, the composition ratio ishigh between the anionizing element, e.g., Te, and an ionizing element,e.g., Al. As such, with the intermediate layer provided, the movableions are to move with more ease, but on the other hand, the excessivemovement of the movable ions causes the excessive formation of Aloxides, thereby resulting in a tendency of increasing the elementresistance together with the resistance value of the intermediate layeritself.

For increasing the capacity of the memory, microfabricating the memoryelements and the drive transistors configuring the memory is expected asdescribed above. However, if the transistors are microfabricated asabove, the drive current shows a decrease. In consideration thereof, forincreasing the capacity of the memory, expected are memory elementsoperatable at a low current.

With the memory element configured as above, decreasing the elementresistance allows the operation at a low current. For decreasing theelement resistance, the intermediate layer may be made thinner. However,if the intermediate layer where movable ions are easy to move is madethinner as such, the effect to be produced by the resulting intermediatelayer, i.e., the effect of allowing the movable ions to move with moreease is diminished. This causes a difficulty in switching at a lowcurrent, e.g., a change of resistance value from the high-resistancestate to the low-resistance state, thereby impairing the elementcharacteristics for writing and erasing, for example. As such, theintermediate layer is expected to be made thicker to decrease theresistance value. The issue here is that, however, when the intermediatelayer is made thicker as described above, an oxide film is formed easilybecause the movable ions move onto the lower electrode, and thus theelement resistance is disadvantageously increased.

On the other hand, with the memory element 1 of this embodiment, the ionsource layer 21 and the intermediate layer 23 are provided therebetweenwith the barrier layer 22 containing a transition metal or a nitridethereof. Such a structure favorably prevents the movement of movableions (e.g., Al ions) to be provided excessively from the ion sourcelayer 21. This accordingly prevents the formation of a metallic oxidefilm, e.g., AlOx, on the surface of the lower electrode 10.

As described above, with the memory element 1 of the embodiment, the ionsource layer 21 and the intermediate layer 23 are provided therebetweenwith the barrier layer 22 containing a transition metal or a nitridethereof. Such a structure favorably prevents the movement of movableions (e.g., Al ions) to be provided excessively from the ion sourcelayer 21. This accordingly prevents the formation of a metallic oxidefilm, e.g., AlOx, on the surface of the lower electrode 10. In otherwords, this allows the intermediate layer 23 to remain thick, andprevents any possible increase of the element resistance. As such, thecharacteristics of data writing and erasing to/from the memory element 1are improved with the memory element 1 remained low in resistance value.

(Memory Device)

By arranging a plurality of memory elements 1 described above in rows orin a matrix, for example, a memory device (memory) is possiblyconfigured. At this time, as appropriate, the memory elements 1 may beeach connected, with a MOS transistor for element selection use or witha diode to configure a memory cell. The resulting memory cells may bethen each connected to a sense amplifier, an address decoder, circuitsof writing, erasing, and reading, and others by wiring.

FIGS. 2 and 3 each show an exemplary memory device (memory cell array)including a large number of memory elements 1 arranged in a matrix. FIG.2 shows the cross-sectional configuration of the memory cell array, andFIG. 3 shows the configuration thereof in a planar view. In this memorycell array, to each of the memory elements 1, wiring connected to thelower electrode 10 side thereof is so provided as to intersect wiringconnected to the upper electrode 30 side thereof, and at the respectiveintersection points, the memory element 1 is disposed.

The memory elements 1 all share the layers, i.e., the resistance changelayer 24, the ion source layer 21, and the upper electrode 30. In otherwords, these layers, i.e., the resistance change layer 24, the ionsource layer 21, and the upper electrode 30, are each for the shared useby all of the memory elements 1 (are each one specific layer for use byall of the memory elements 1). The upper electrode 30 is a plateelectrode PL for shared use by any adjacent cells.

On the other hand, the lower electrode 10 is provided individually toeach of the memory cells so that the memory cells are electricallyseparated from one another. As such, the memory elements 1 in the memorycells are each defined by position to correspond to its lower electrode10. The lower electrodes 10 are each connected to its corresponding MOStransistor Tr for cell selection use, and the memory elements 1 are eachdisposed above its corresponding MOS transistor Tr.

The MOS transistor Tr is configured by source/drain regions 43, and agate electrode 44, which are formed in a region separated by an elementseparation layer 42 in the substrate 41. A side wall insulation layer isformed on the wall surface of the gate electrode 44. The gate electrode44 serves also as a word line WL, which is one of two pieces of addresswiring for the memory element 1. One of the source/drain regions 43 ofthe MOS transistor Tr is electrically connected to the lower electrode10 of the memory element 1 via various layers, i.e., a plug layer 45, ametal wiring layer 46, and a plug layer 47. The other of thesource/drain regions 43 of the MOS transistor Tr is connected to themetal wiring layer 46 via the plug layer 45. The metal wiring layer 46is connected to a bit line BL (refer to FIG. 3), which is the remainingpiece of address wiring for the memory element 1. Note that, in FIG. 3,an active region 48 of the MOS transistor Tr is indicated by alternatelong and short dashed lines. In the active region 48, contact sections51 are connected to the lower electrode 10 of the memory element 1, andcontact sections 52 are each connected to the bit line BL.

In such a memory cell array, when a voltage is applied to the bit linesBL with the gate of the MOS transistor Tr turned ON by the word line WL,the voltage is directed to the lower electrode 10 of the selected memorycell via the source/drain of the MOS transistor Tr. In this example, asfor the voltage applied to the lower electrode 10, when the polaritythereof is at a negative potential compared with the potential of theupper electrode 30 (the plate electrode PL), the resistance value of thememory element 1 is changed in state to low resistance as describedabove, whereby the selected memory cell is written with information.Next, when the potential of the voltage applied this time to the lowerelectrode 10 is positive compared with the potential of the upperelectrode 30 (the plate electrode PL), the resistance value of thememory element 1 is changed in state again to high resistance, wherebythe information written to the selected memory cell is erased. Forreading of the written information, for example, a selection of memorycell is made by the MOS transistor Tr, and with respect to the selectedmemory cell, a predetermined level of voltage or current is applied. Thecurrent or voltage varying in level based on the resistance state of thememory element 1 at this time is detected via a sense amplifier orothers connected to the tip of the bit line BL or of the plate electrodePL. Herein, the voltage or current for application to the selectedmemory cell is set to be smaller than the threshold value of the voltageor others at which the memory element 1 shows a change of resistancevalue.

The memory device of this embodiment is applicable to various types ofmemory devices as described above. For example, the memory device isapplicable for use with any types of memories such as once-writablePROM, electrically erasable EEPROM, or so-called RAM available forhigh-speed writing, erasing, and reproduction.

(Modification)

FIG. 4 is a cross-sectional view of a memory element 2 in a modificationof the present disclosure, showing the configuration thereof. Anyconfiguration component similar to that of the embodiment describedabove is provided with the same reference numeral, and is not describedagain. The memory element 2 includes the lower electrode 10 (firstelectrode), a memory layer 60, and the upper electrode 30 (secondelectrode) in this order. The memory layer 60 is in the structuredifferent from that in the embodiment, i.e., is in the layered structureincluding an ion source layer 61, an intermediate layer 63, a barrierlayer 62, and a resistance change layer 64, which are disposed one onthe other in this order from the upper electrode 30 side.

The ion source layer 61 is in the structure similar to that of the ionsource layer 21 described above, i.e., includes at least one oftransition metals in a group of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and Wtogether with Al, Cu, silver (Ag), zinc (Zn) that is to be cationized,and a chalcogen element that is to be anionized.

The intermediate layer 63 and the resistance change layer 64 arerespectively in the structures similar to those of the intermediatelayer 23 and the resistance change layer 24 described above.Specifically, the intermediate layer 63 is made of a cationic componentand a movable anionic component, and in addition to AlTe, for example,CuTe, ZnTe, AgTe, or MgTe will also do. Moreover, as an alternative toTe, the anionic component therein may be a chalcogen element such assulfur (S) or selenium (Se). The resistance change layer 64 is made ofan oxide, oxinitride, or nitride containing at least one of thetransition metal elements including Ti, Zr, Hf, Ta, W, and others, andan oxide of Al, Cu, Ag, and Zn being movable ions. Alternatively, theresistance change layer 64 may contain an oxide of high-resistancerare-earth elements including Ge, Mg, and Si.

The barrier layer 62 is for controlling the movement of the movable ionsfrom the ion source layer 61 to the lower electrode side, and isdisposed between the intermediate layer 63 and the resistance changelayer 64. Such a barrier layer 62 is made of at least one transitionmetal or a nitride thereof similarly to the barrier layer 22 describedabove. To be specific, such a material is exemplified by Cu, Ti, Zr, Hf,V, Nb, Ta, Cr, Mo, and W. Moreover, the barrier layer 62 preferably hasthe film thickness thicker than 0.1 nm but thinner than 1 nm.

In the memory element 2 in this modification, with the barrier layer 62disposed between the intermediate layer 63 and the resistance changelayer 64, the effect similar to that achieved with the memory element 1in the embodiment above is possibly achieved.

EXAMPLES

In the below, specific examples of the present disclosure are described.

The memory elements 1 and 2 of FIGS. 1 and 4 were respectivelymanufactured similarly to the memory elements in the embodimentdescribed above. First of all, the lower electrode 10 made of TiN with atransistor incorporated in the base was subjected to cleaning and plasmaoxidation by argon plasma. The memory layer 20 or 60, and the upperelectrode 30 were formed on the resulting lower electrode 10 using adevice for sputtering. The electrode diameter was 150 nmφ. The layermade of alloy was formed at the same time using a target of thecomponent element. Thereafter, the upper electrode 30 was subjected toetching on the surface, and therefore a wiring layer (Al layer) with thethickness of 200 nm is formed for a connection to the contact portionwhere an external circuit was connected for provision of an intermediatepotential (Vdd/2). Thereafter, in a furnace for a vacuum heat treatment,the resulting structure was subjected to a heat treatment for two hoursat the temperature of 340° C. as a post annealing treatment. In thismanner, the memory cell arrays shown in FIGS. 2 and 3 were manufacturedwith various compositions and film thicknesses, and the results wereused as Experimental Samples 1 to 12. Herein, the resistance changelayers 24 and 64 formed by plasma oxidation each have the film thicknessof about 1 nm after the analysis by XRR (X-Ray Reflectometer) or XPS(X-Ray Photoelectron Spectroscopy).

In these Experimental Samples 1 to 12, the upper wiring patternconnected to the upper electrode 30 was grounded at the intermediatepotential of Vdd/2, and then a voltage was applied to the gate electrodeof any selected memory cell, i.e., to the word line WL, so that thestate was changed to ON. Thereafter, the “operation of writing” wasperformed to the memory cell array of 4 kbit, and then reading of theresistance value was performed. The “operation of writing” was anoperation of applying a voltage of 3.0 V with a pulse width of 10 ns,and with a current for writing of about 100 μA to, in the source/drain13 of the transistor Tr, the electrode connected to the one of those notconnected to the memory element 1, i.e., to the bit line BL. Next, avoltage was applied to the gate electrode to change the state to ON, andthen performed was the “operation of erasing”, which was an operation ofapplying a voltage of 2.0 V with the pulse width of 10 ns, and with acurrent for erasing of about 100 μA. After such an operation of erasing,the resistance value in the state of erasing was read. Thereafter, byperforming writing (low-resistance state) and erasing (high-resistancestate) of the memory cell array by 2 kbit, the distribution ofresistance in the respective states was checked also with the operationratio for bits allowing writing to a resistance value of 10 kΩ or lower.

In Experimental Samples 1 to 12, the composition of each layer was asbelow. In Experimental Samples 1, and 4 to 7, the layers were stacked inorder of “lower electrode/resistance change layer/intermediatelayer/barrier layer/ion source layer/upper electrode”, and inExperimental Samples 8 to 12, the layers were stacked in order of “lowerelectrode/resistance change layer/barrier layer/intermediate layer/ionsource layer/upper electrode”. Note that in Experimental Samples 2 and3, no barrier layer was provided. In Experimental Samples 1 to 12, theresistance change layer (TiOx) had the film thickness of about 1 nm, andAlOx was self-generated with the thickness of 1 to 2 nm so that theresulting layer was the resistance change layer 24 or 64. The ion sourcelayers 21 and 61 each had the film thickness of 60 nm, and the upperelectrode (W) 30 had the film thickness of 50 nm. The film thickness ofthe barrier layers 22 and 62, and that of the intermediate layers 23 and63 are shown in Table 1.

-   (Experimental Sample 1) TiN/TiOx/Te/Zr/CuZrTeAlGe/W-   (Experimental Sample 2) TiN/TiOx/Te/CuZrTeAlGe/W-   (Experimental Sample 3) TiN/TiOx/Te/CuZrTeAlGe/W-   (Experimental Sample 4) TiN/TiOx/Te/Zr/CuZrTeAlGe/W-   (Experimental Sample 5) TiN/TiOx/Te/Zr/CuZrTeAlGe/W-   (Experimental Sample 6) TiN/TiOx/Te/Zr/CuZrTeAlGe/W-   (Experimental Sample 7) TiN/TiOx/Te/Zr/CuZrTeAlGe/W-   (Experimental Sample 8) TiN/TiOx/CuZr/Te/CuZrTeAlGe/W-   (Experimental Sample 9) TiN/TiOx/CuZr/Te/CuZrTeAlGe/W-   (Experimental Sample 10) TiN/TiOx/CuZr/Te/CuZrTeAlGe/W-   (Experimental Sample 11) TiN/TiOx/CuZr/Te/CuZrTeAlGe/W-   (Experimental Sample 12) TiN/TiOx/CuZr/Te/CuZrTeAlGe/W

Table 1 is a list of writing availability ratio based on the filmthickness of the barrier layers 22 and 62 and that of the intermediatelayers 23 and 63 in Experimental Samples 1 to 12, the erasing resistance(median of the resistance values in the high-resistance state), and thecumulative frequency distribution. FIGS. 5A to 5F each show theresistance distribution (cumulative frequency distribution) after therepeated tests in Experimental Samples 1 to 12.

TABLE 1 Writing Intermediate Barrier Erasing Availability Layer (nm)Layer (nm) Resistance (Ω) Ratio (%) Experimental 10 0.5 430M 99.9 Sample1 Experimental 10 — 430M 2 Sample 2 Experimental 5 — 87M 99.95 Sample 3Experimental 5 0.1 26M 99.95 Sample 4 Experimental 5 0.3 8.2M 99.95Sample 5 Experimental 5 0.7 3.6M 99.9 Sample 6 Experimental 5 1 8.7M99.95 Sample 7 Experimental 10 1 71k 97.3 Sample 8 Experimental 5 0.148M 99.95 Sample 9 Experimental 5 0.3 15M 99.9 Sample 10 Experimental 50.5 4.5M 99.95 Sample 11 Experimental 5 0.8 63k 67.7 Sample 12

First of all, a comparison of writing availability ratio was made amongExperimental Samples 1 to 3. In Experimental Sample 3 with theintermediate layer 23 having the film thickness of 5 nm, the writingavailability ratio was 99.95% or higher. In contrast to this, inExperimental Sample 2 with the intermediate layer 23 having the filmthickness of 10 nm, the writing availability ratio was only about 2%.This seems to be because, as is evident from FIG. 5B, the intermediatelayer 23 increased in film thickness caused an increase of the elementresistance, and the writing threshold voltage and current were thusincreased, thereby resulting in a failure of writing. On the other hand,in Experimental Sample 1, the intermediate layer 23 had the filmthickness of 10 nm similarly to that in Experimental Sample 3, but thewriting availability ratio was 99.9%, and the operation characteristicswere satisfactory. This seems to be because, by providing the Zr-madebarrier layer 22 on the interface between the ion source layer 21 andthe intermediate layer 23, any excessive diffusion of Al ions wasprevented toward the lower electrode 10 side. This accordingly preventedthe formation of a high-resistance film (AlOx) on the interface betweenthe lower electrode 10 and the resistance change layer 24 so that theelement resistance seems to be controlled not to be increased.

Next, a comparison of operation at a low current was made betweenExperimental Samples 1 and 3. FIGS. 7A and 7B show the result of alow-current repetition endurance test up to the repetition of 10⁶. Thetest was performed to Experimental Sample 1 (FIG. 7A) and ExperimentalSample 3 (FIG. 7B) with the applied voltage during writing/erasing of3.0 V/2.0 V, the pulse width during writing/erasing of 10 ns/10 ns, andthe current of 50 μA. In Experimental Sample 1, the data retentioncharacteristics remained satisfactory with the repetition of 10⁶ ormore. On the other hand, in Experimental Sample 3, the data retentioncharacteristics were lost with the repetition of about 10². This seemsto be due to the thickness of the intermediate layer 23. In ExperimentalSample 1 in which the intermediate layer 23 was a layer made of Te withthe thickness of 10 nm, a layer of AlTe was formed immediately after theformation of the ion source layer because Al ions were easily moved. Athicker AlTe layer brought a higher resistance, and by the AlTe layer, ahigh level of voltage bias was divided, thereby producing an effect offacilitating the movement of the Al ions. As such, the Al-madeconductive path formed in the resistance change layer 24 during theoperation of erasing was more likely to put back to the ion source layer21. This is the reason why Experimental Sample 1 shows the bettererasing characteristics than those in Experimental Sample 3.

With the barrier layer 22 provided as above, even if the intermediatelayer 23 was increased in film thickness, any excessive diffusion of Alions to the lower electrode 10 side was favorably prevented, and anyoverwriting of the element resistance was prevented without impairingthe mobility of the Al ions. In other words, with the barrier layer 22provided as such, the resulting memory element 1 was low in resistance,and at the same time, have the low-current operation characteristics.

By referring to Experimental Samples 1, and 4 to 7, described next isthe relationship between the film thickness of the barrier layer 22, themedian resistance, and the resistance separation width. FIGS. 8A and 8Beach show, based on the results of FIGS. 5A, 5D to 5F, and FIG. 6A, therelationship between the film thickness of the barrier layer 22 and themedian resistance (FIG. 8A), and the relationship between the filmthickness of the barrier layer 22 and the resistance separation width(FIG. 8B). As is known from FIG. 8A, the median resistance was reducedas the barrier layer 22 was increased in film thickness. In other words,the provision of the barrier layer 22 prevented the element resistancefrom increasing. However, as is known from FIG. 8B, if the barrier layer22 had the film thickness being too thick, the resistance separationwidth was reduced, and the resistance separation characteristics wereimpaired. Since the intermediate layer 23 in Experimental Sample 1 wastwice thicker than those in Experimental Samples 4 to 7, the elementresistance was easily assumed to be high. As such, the film thickness ofthe barrier layer 22 was preferably thicker at least than 0.1 nm butthinner than 1 nm to allow the memory element 1 to be low in resistance,and at the same time, to have the low-current operation characteristics.

Described next is the relationship between the film thickness, themedian resistance, and the resistance separation width in ExperimentalSamples 8 to 12 in which the barrier layer 62 is disposed between theintermediate layer 63 and the resistance change layer 64. FIGS. 9A and9B each show, based on the results of FIGS. 6B to 6F, the relationshipbetween the film thickness of the barrier layer 62 and the medianresistance (FIG. 9A), and the relationship between the film thickness ofthe barrier layer 62 and the resistance separation width (FIG. 9B). Asis known from FIG. 9A, the median resistance was reduced as the barrierlayer 62 was increased in film thickness similarly to those inExperimental Samples 1, and 4 to 7 described above. To be specific,Experimental Samples 8 and 11 respectively show the resistance of 4.5 MΩand 71 kQ which were smaller compared with Experimental Sample 3 (87 MΩ)in which the barrier layer 64 was not provided. However, in ExperimentalSample 12 in which the barrier layer had the thickness of 1 nm, sincethe element resistance was decreased too much, the writing availabilityratio was decreased as shown in FIG. 6F. Specifically, although thewriting availability ratio in Experimental Samples 8 to 11 was 99.9% orhigher, Experimental Sample 12 shows the lower writing availabilityratio, i.e., 67.7%. As such, similarly to Experimental Samples 1, and 4to 7 described above, the film thickness of the barrier layer 62 waspreferably thicker at least than 0.1 nm but thinner than 1 nm to allowthe memory element 2 to be low in resistance, and at the same time, tohave the low-current operation characteristics.

Furthermore, based on the results of FIGS. 8A and 8B, and those of FIGS.9A and 9B, with the barrier layers 22 and 62 provided as such,irrespective of the position and material thereof, the memory elements 1and 2 are known to be reduced in element resistance, and to have thebetter low-current operation characteristics.

While the present disclosure has been described in detail by referringto the embodiment, modification, and Examples, the present disclosure isnot restrictive to the embodiment and others described above, and it isunderstood that numerous other modifications may be possibly devised.

For example, in the embodiment and modification above, theconfigurations of the memory elements 1, 2, and that of the memory cellarray are specifically described. However, all of the layers are notnecessarily provided, or any other layers may be also provided. To bespecific, in the embodiment and modification above, exemplified is thecase of providing a piece of the barrier layer 22 (62) between the ionsource layer 21 and the intermediate layer 23 (between the intermediatelayer 63 and the resistance change layer 64). Alternatively, the barrierlayer 22 (62) may be provided respectively between the ion source layerand the intermediate layer, and between the intermediate layer and theresistance change layer.

Moreover, for example, the materials of the layers, the film-formingmethods and conditions, and others described in the embodiment andothers above are surely not restrictive, and any other materials, or anyother film-forming methods will also do. For example, the ion sourcelayers 21 and 61 may be each added with any other types of transitionmetal element such as Ti, Hf, V, Nb, Ta, Cr, Mo, or W as long as thecomposition ratio described above remains the same, and other than Cu,Ag, and Zn, nickel (Ni) may be added.

The present disclosure contains subject matter related to that disclosedin Japanese Priority Patent Application JP 2011-61628 filed in the JapanPatent Office on Mar. 18, 2011, the entire content of which is herebyincorporated by reference.

It should be understood by those skilled in the art that variousmodifications, combinations, sub-combinations, and alterations may occurdepending on design requirements and other factors insofar as they arewithin the scope of the appended claims or the equivalents thereof.

What is claimed is:
 1. A memory element, comprising: a first electrode,a memory layer, and a second electrode in this order, wherein, thememory layer includes (a) a resistance change layer on the firstelectrode, (b) an ion source layer, (c) an intermediate layer betweenthe resistance change layer and the ion source layer, and (d) a barrierlayer between the ion source layer and the intermediate layer or betweenthe intermediate layer and the resistance change layer, the barrierlayer having a surface in contact with the intermediate layer.
 2. Thememory element according to claim 1, wherein the barrier layer containsone or more of copper (Cu), titanium (Ti), zirconium (Zr), hafnium (Hf),vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum(Mo), or tungsten (W) as the at least one transition metal.
 3. Thememory element according to claim 1, wherein the barrier layer has afilm thickness thicker than 0.1 nm but thinner than 1 nm.
 4. The memoryelement according to claim 1, wherein the ion source layer contains atleast one ionizing metallic element selected from the group consistingof aluminum (Al), copper (Cu), silver (Ag), and zinc (Zn), and one ormore of oxygen (0), tellurium (Te), sulfur (S), and selenium (Se). 5.The memory element according to claim 4, wherein the barrier layer iseffective in controlling a movement of mobile ions of the at least oneionizing metallic element to the first electrode.
 6. The memory elementaccording to claim 1, wherein the intermediate layer is an electrolytelayer having a resistance higher than that of the ion source layer, andis enabled to receive mobile ions of an ionizing metallic element. 7.The memory element according to claim 1 wherein the intermediate layercontains at least a chalcogen element selected from the group consistingof Te, S and Se.
 8. The memory element according to claim 7, wherein theintermediate layer contains Te and Al.
 9. The memory element accordingto claim 1, wherein the resistance change layer contains (i) an oxide ofa metallic element formed by a diffusion of mobile ions of the metallicelement from at least one of the ion source layer and the intermediatelayer, and (ii) an oxide of a transition metal.
 10. The memory elementaccording to claim 1, wherein the resistance change layer: (i) is in alayered structure including (a) a layer containing an aluminum oxideformed by diffusion of Al contained at least either in the ion sourcelayer or in the intermediate layer, and (b) a layer containing an oxideof a transition metal, or (ii) is in a mixed structure of the aluminumoxide and the oxide of a transition metal.
 11. The memory elementaccording to claim 1, wherein a change of resistance value occurs byformation of a low-resistance section including a metallic element inthe resistance change layer in response to application of a voltage tothe first and second electrodes.
 12. A memory device, comprising: aplurality of memory elements, each memory element including a firstelectrode, a memory layer, and a second electrode in this order; and apulse application section applying a voltage or current pulseselectively to the memory elements, wherein, the memory layer includes(a) a resistance change layer on the first electrode, (b) an ion sourcelayer, (c) an intermediate layer between the resistance change layer andthe ion source layer, and (d) a barrier layer between the ion sourcelayer and the resistance change layer, the barrier layer having asurface in contact with the intermediate layer.
 13. The memory deviceaccording to claim 12, wherein the barrier layer contains one or more ofcopper (Cu), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V),niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), or tungsten(W) as the at least one transition metal.
 14. The memory device of claim12, wherein the barrier layer is between the ion source layer and theintermediate layer.
 15. The memory device of claim 12, wherein thebarrier layer is between the intermediate layer and the resistancechange layer.
 16. The memory device of claim 12 where the intermediatelayer contains, at least a chalcogen element selected from the groupconsisting of tellurium (Te), sulfur (S), and selenium (Se).
 17. Thememory device of claim 12 wherein the barrier layer contains atransition metal.